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Preparation of porous composite hydrogel with ultra-high dye adsorption ca‐

pacity based on biochar: Adsorption behaviors and mechanisms

Keran Li, Jie Wu, Xin Li, Baidan Li, Dahua Zhou

PII: S0009-2509(24)00415-9
DOI: https://doi.org/10.1016/j.ces.2024.120115
Reference: CES 120115

To appear in: Chemical Engineering Science

Received Date: 18 December 2023

Revised Date: 20 March 2024
Accepted Date: 9 April 2024

Please cite this article as: K. Li, J. Wu, X. Li, B. Li, D. Zhou, Preparation of porous composite hydrogel with
ultra-high dye adsorption capacity based on biochar: Adsorption behaviors and mechanisms, Chemical
Engineering Science (2024), doi: https://doi.org/10.1016/j.ces.2024.120115

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 Preparation of porous composite hydrogel with ultra-high dye

adsorption capacity based on biochar: adsorption behaviors and

mechanisms

Keran Li a, b,*, Jie Wu a, Xin Lia, Baidan Lia, Dahua Zhou c ,*

aCollege of Chemistry and Chemical Engineering, Southwest Petroleum University,

Chengdu, 610500, PR China
bState Key Laboratory of Polymer Materials Engineering, Sichuan University,
Chengdu, 610500, PR China
c-Chongqing Intelligent Technology, Chinese Academy of Green and Intelligent
Technology, Chinese Academy of Sciences, Chongqing 400714, China

Keran Li - College of Chemistry and Chemical Engineering, Southwest Petroleum

University, Chengdu, 610500, Sichuan, China; Tel: +86 028 83037306; fax: +86 028
8303 7305; E-mail address: [email protected]

Dahua Zhou - Chongqing Intelligent Technology, Chinese Academy of Green and

Intelligent Technology, Chinese Academy of Sciences, Chongqing 400714, China;
Email: [email protected]

1
Abstract

With the continuous development of industrialization, dyes in industrial wastewater

have become a serious environmental issue. To address this environmental issue, a
biochar-based composite hydrogel (PAS/aBC-CD) was designed. The use of a simple
composite method effectively resolves the challenge of biochar recovery. Furthermore,
the modified adsorbent exhibits remarkably high adsorption capacities for all three dyes
(MB: 1494 mg/g, MG: 1182 mg/g, and NR: 1031.6 mg/g). It is noteworthy that binary
co-adsorption experiments have demonstrated that CrO42- can act as a bridging agent to
enhance the adsorption of dyes by the adsorbent. Systematic adsorption-desorption
experiments have demonstrated the outstanding recyclability of PAS/aBC-CD,
maintaining 98% of its adsorption capacity after 5 cycles. Additionally, its industrial
application potential was demonstrated through column adsorption experiments. In
conclusion, this study utilized a simple composite method to produce an adsorbent with
high adsorption performance and industrial application potential.

Keywords: hydrogel; biochar; adsorption; cationic dyes

1. Introduction
Dye molecules are characterized by the presence of polar groups, making them highly
soluble in water and capable of tightly binding to substrates with anionic charges, such
as textile fibers[1]. Therefore, these dye molecules are widely used in the textile,
papermaking, and plastic manufacturing industries[2]. The discharge of industrial
wastewater(e.g., brine) can have serious implications for human health and water
quality[3]. Firstly, if these dye molecules persist in the aquatic environment for extended
periods, they may be absorbed by organisms, leading to bioaccumulation and
biomagnification along the food chain[4]. This ultimately poses risks to human health,
such as carcinogenicity and reproductive toxicity[5]. Secondly, an excessive amount of
dye molecules may disrupt aquatic ecosystems, primarily manifesting as reduced
biodiversity of aquatic organisms, depletion of dissolved oxygen, and the proliferation
of toxic algae[6,7]. Therefore, these textile wastewater cannot be reused for drinking
water or industrial water purposes[8,9]. To mitigate these risks, several techniques have
been developed for the removal of cationic dyes from water, including catalytic
degradation, chemical reduction[10], ion exchange[11], membrane filtration[12], and
adsorption. Among these methods, adsorption is widely researched and applied due to
its simplicity, low cost, and high efficiency in pollutant removal[13].

Among the plethora of adsorbent materials available, biochar has emerged as a widely
utilized adsorbent material[14]. Its abundant porous structure endows it with a significant
specific surface area, thereby affording ample attachment sites for the adsorption of
pollutants. However, the inherent functional groups of pure biochar materials are often

2
insufficient, necessitating further surface modification of the raw materials or the
finished biochar product. In existing research, the majority of scholars have employed
methods such as acid treatment[15] (HNO3, H2SO4), alkali treatment[16] (KOH), metal
doping (Fe), among others, to modify the raw materials of biochar. For example,
Saeed[17] reported a seaweed-derived biochar treated with sulfuric acid, exhibiting a
maximum adsorption capacity of only 133.33 mg/g for the cationic dye MB. jjellali[18]
employed KOH activation on industrial sludge-derived biochar, demonstrating a
maximum adsorption capacity of 65.9 mg/g for the cationic dye MB. While acid or
alkali modification increases the presence of oxygen-containing functional groups on
the surface of biochar, its adsorption capacity remains limited[19]. Hence, this study
focuses on pollutants containing a high proportion of aromatic ring structures.
Therefore, N-doping is selected to construct aromatic rings with varying degrees of
aromacity, thereby enhancing the adsorption potential of biochar for target molecules.

Furthermore, surface modification of biochar can directly increase its surface functional
groups. For instance, Ahmed[20] utilized biochar prepared from orange peel, followed
by surface modification with TETA, resulting in a maximum adsorption capacity of
384.62 mg/g for Acid Yellow. Sivakumar[21] employed chitosan to modify biochar
derived from wood apple peel, achieving a maximum adsorption capacity of 53.35 mg/g
for Malachite Green. Therefore, surface modification represents a reliable approach for
enhancing adsorption performance. Cyclodextrins are a class of cyclic compounds
characterized by hydrophilic outer surfaces and hydrophobic internal cavities[22]. Its
unique molecular structure allows it to encapsulate pollutant molecules through host-
guest interactions[23]. Simultaneously, the abundant hydroxyl groups on its surface not
only serve as effective adsorption sites but also function as anchoring points for
attaching to the surfaces of other materials. Moreover, research on surface modification
of biochar using cyclodextrins is relatively scarce. Therefore, this study opts to utilize
cyclodextrins as the surface modifier.

The separation of biochar powder from environmental media often requires additional
steps such as centrifugation or filtration. The processing of biochar may also result in
secondary pollution[24]. Previous studies have utilized magnetic nanoparticles loaded
onto the surface of biochar; however, this approach may lead to pore blockage,
consequently reducing adsorption effectiveness[25]. For example, Şerife [26] et al.
utilized acorn cups to prepare magnetic biochar loaded with Fe3O4, achieving a
maximum adsorption capacity of 52.63 mg/g for MB, and it maintains 83% adsorption
capacity after 5 cycles. Yan[27] prepared magnetic particle-loaded biochar using a
simple secondary grinding loading method, achieving a removal rate of 85 mg/L for
MG. After cycling, it maintained 93.6% of its adsorption capacity. Therefore, the
optimization of the recyclability of biochar remains a priority for further advancement.
Therefore, composite biochar materials may emerge as an effective method for
enhancing the recyclability of biochar. In this study, hydrogels are chosen as composite
agents, dispersing biochar within the gel network formed by monomeric materials[28].
Consequently, this approach enhances the recyclability of biochar. Moreover, the
abundant and adjustable monomeric species of hydrogels can further enhance the
3
flexibility of composite biochar-based gel materials.

In this study, walnut shells are utilized as raw materials, with urea serving as the
nitrogen source for preparing N-doped biochar. Subsequently, β-cyclodextrin is
employed for surface modification. Finally, the modified biochar is dispersed within a
gel network comprising acrylic acid (AA) and sodium styrene sulfonate (SSS)，named
as PAS/aBC-CD hydrogel. FTIR and TGA analysis techniques were employed to
analyze the functional group structures of the adsorbent, while SEM was utilized to
observe the surface morphology of the adsorbent. The adsorption performance of
PAS/aBC-CD hydrogel was studied using three cationic dyes, namely Methylene Blue
(MB), Malachite Green (MG), and Neutral Red (NR). The influence of factors such as
composite ratio, pH value, and adsorption temperature on the performance of the
adsorbent was discussed. The molecular diffusion process and adsorption mechanism
were analyzed using kinetic models and isotherm models, respectively. The application
potential of PAS/aBC-CD hydrogel was explored through column adsorption, co-
adsorption, and adsorption in real water samples.

2. Materials and methods

2.1 Materials

Information about the materials used in this paper is displayed in the supporting
information.

2.2 Preparation of the adsorbent

2.2.1 Preparation of acidified biochar (aBC)

The precursor material for biochar was selected as walnut shell. The preparation method
involved mixing 1 g of dried walnut shell powder with 1.5 g of urea in a beaker,
followed by addition of 10 mL of ultrapure water and sonication to achieve
homogeneity. The resulting mixture was dried to a paste-like consistency. Subsequently,
under continuous nitrogen flow protection, the sample was activated and carbonized at
700°C for 1 hour, resulting in the production of biochar (BC).

A mixture of 98% H2SO4 and 65% HNO3 was prepared in a 3:1 volume ratio to obtain
a 160 mL mixed acid solution. The mixed acid solution was then cooled to room
temperature, and 4.0 g of biochar powder was added for acidification reaction. The
reaction was carried out in an oil bath at a temperature of 80 °C. After the completion
of the reaction, the resulting solid was washed multiple times with ultrapure water,
followed by vacuum drying at 60 °C for 24 hours. This process resulted in the
production of acidified biochar (aBC).
4
2.2.2 Preparation of cyclodextrin-modified biochar (aBC-CD)

Next, β-CD was grafted onto aBC through esterification reaction. In detail, 0.5 g of β-
CD and 0.5 g of acidified biochar were dissolved in 80 mL of DMF. The mixture was
sonicated to disperse the biochar evenly, followed by the addition of 6.0 g of
dicyclohexylcarbodiimide and 2.0 g of 4-dimethylaminopyridine. The esterification
reaction was carried out in an oil bath at 25 °C for 24 hours. After the reaction, the
resulting solid was washed several times with DMF and ultrapure water, and then
vacuum-dried at 60°C for 48 hours. The resulting solid product was labeled aBC-CD.

2.2.3 Preparation of composite hydrogel (PAS/aBC-CD)

First, 0.075 g of aBC-CD was dispersed in 2.5 mL of ultrapure water using an ultrasonic
homogenizer in a centrifuge tube. Then, the monomers acrylic acid (AA) and sodium
styrene sulfonate (SSS) were sequentially added to the mixture. Then sodium dodecyl
benzene sulfonate was added. After ultrasonic treatment for 5 minutes, N,N'-
methylenebisacrylamide and tetramethylethylenediamine were added. After five
minutes of ultrasonic treatment, the initiator was added with azodiisobutyronitrile and
the reaction was carried out for four hours under weak stirring in an oil bath at 80℃.
After the reaction was completed, the solid was freeze-dried to obtain the PAS/aBC-
CD hydrogel.

2.3 Analysis

The details of the analyzed experiments used are shown in the supporting information.

2.4 Adsorption experiment

All adsorption experiment details are displayed in the supporting information.

2.5 Adsorption kinetics and thermodynamics

In order to investigate the kinetic behavior of PAS/aBC-CD hydrogel, this study

conducted kinetic adsorption experiments on three cationic dyes (MB, MG, and NR).
200 mg of PAS/aBC-CD hydrogel was added to 200 mL of dye solution, and the
concentration of each dye solution was 100 ppm, with adsorption experiments
conducted at their respective optimal pH values. The absorbance of the solution was
measured within a fixed time range, and the amount of adsorbent adsorbed at time t, 𝑞𝑡
was calculated based on equation (1). To accurately described the process of adsorption,
this study used the nonlinear forms of the pseudo-first-order (PFO) [29]and pseudo-
second-order (PSO)[29] kinetic models for fitting, with the calculation formulas for both

5
models shown in equation (2-3). Additionally, in order to better understand the mass
transfer process and rate-limiting step of dye molecules between liquid and solid phases,
this study analyzed the entire adsorption process of the three dyes using the interparticle
diffusion model[30] and liquid film diffusion model[31,32], with their calculation formulas
presented below:

𝐶0 ― 𝐶𝑒
𝑞𝑡 = (1)
𝐶0

PFO: 𝑞𝑡 = 𝑞𝑒(1 ― 𝑒―𝑘1𝑡 ) (2)

𝑡𝑘2𝑞2𝑒
PSO: 𝑞𝑡 = 1 𝑡𝑞𝑒𝑘2
(3)

Interparticle diffusion model: 𝑞𝑡 = 𝑘𝑖𝑑𝑡1/2 +𝐶 (4)

Liquid film diffusion model: 𝑙𝑛(1 ― 𝐹) = 𝐶1 ― 𝑘𝑓𝑑𝑡 (5)

Here, 𝑘1 (min-1) was the rate constant for the PFO kinetic model, while k2 (g·mg-
1·min-1) was the rate constant for the PSO model. 𝑞 -1 -1
𝑒 (mg·g ) and 𝑞𝑡 (mg·g )
represent the amount of dye adsorbed and the adsorption time respectively. k𝑖𝑑 (mg·g-
1·min-0.5) was the rate constant for interparticle diffusion at different stages, C (mg/g)

was the constant related to the boundary layer, F was the solute fraction adsorbed at
any time, which equaled 𝑞𝑡 divided by 𝑞𝑒. k𝑓𝑑 (min-1) was the rate of liquid film
diffusion, and C1 (g·mg-1) was the rate constant for liquid film diffusion.

Experimental research was conducted on three types of cationic dyes, namely MB, MG,
and NR, in order to investigate the adsorption isotherms and thermodynamic
characteristics of these dyes on hydrogel surfaces. For each dye, 10 mg of PAS/aBC-
CD hydrogel was added to 10 mL solutions with varying concentrations, and they were
adjusted to the optimal pH conditions for adsorption. The experiments were carried out
in a thermostatic oscillator at three different temperatures, namely 298 K, 308 K, and
318 K, and 13 concentration gradients ranging from 40 to 4000 mg/L of dye were set
for each. To determine the adsorption isotherms and explore the adsorption mechanism,
the Freundlich and Langmuir models were used to fitted the experimental data and
calculated the maximum adsorption capacity of the adsorbent.

Additionally, the applicability of the adsorption process was assessed using the RL
calculation formula. RL values greater than 1 indicated that the process was unsuitable,
RL values equal to 0 indicated that the process was irreversible, and RL values between
0 and 1 indicated that the process complied with the Langmuir model[33].

6
In addition to the examination of the adsorption isotherms, the reversibility of the
adsorption process was also examined, and the thermodynamic parameters of
adsorption, including Gibbs free energy, enthalpy, and entropy, were determined[34].
The change in Gibbs free energy (∆G°) determine whether the adsorption process was
spontaneous, while enthalpy (∆H°) and entropy (∆S°) reveal the heat absorption and
orderliness of the process[35,36]. These thermodynamic parameters could provide
valuable insights into the fundamental nature of the adsorption process and its practical
applications. The calculation formula of each model was as follows:

𝐾𝐿𝑞𝑚𝐶𝑒
Langmuir Isotherm model: 𝑞𝑒 = 1 𝐾𝐿𝐶𝑒
(6)

Freundlich Isotherm model: 𝑞𝑒 = 𝐾𝐹𝐶𝑛𝑒 (7)

1
𝑅𝐿 = (8)
1 + 𝐾𝐿𝐶0

∆𝐺° = ―𝑅𝑇𝑙𝑛𝐾𝑐 (9)

∆𝑆° ∆𝐻°
𝑙𝑛 𝐾𝑐 = ― (10)
𝑅 𝑅𝑇

𝑞𝑒
𝐾𝑐 = (11)
𝐶𝑒

where 𝐾𝐿 (L·mg-1) was the adsorption balance constant of the Langmuir model, 𝐾𝐹
(mg (1-1 / n) ·L1 / n·g-1) was the adsorption balance constant of the Freundlich model, 𝑞𝑚
(mg·g-1) was the maximum equilibrium capacity of the Langmuir model, n was the
heterogeneity factor of the Freundlich model, R (8.314 J·mol-1·K-1) was the gas
constant and T (K) was the absolute temperature.

2.6 Absorbent application experiment

In practical applications of adsorbents, the more cycles of adsorption and desorption

that could be performed, the lower the cost of treating dye wastewater, making research
on this material more meaningful. Therefore, this study also investigated the cycling
characteristics of the adsorbent. 0.1 mol/L HCl solution was used for the desorption of
MB, MG, and NR dyes from the adsorbent, and the adsorbent was soaked in the
corresponding eluent for 12 hours after the adsorption of dyes. Then, the adsorbent was
7
washed with copious amounts of ultrapure water. The resulting product was dried in a
vacuum oven at 50 °C for the subsequent adsorption experiments. The cycling
experiments were repeated five times.

To explore the practical application potential of PAS/aBC-CD hydrogel, column

adsorption was chosen as the method of investigation. PAS/aBC-CD hydrogel was
evenly spread into a filter column at a height of 3-4 cm, and cotton was placed beneath
the hydrogel layer to prevent it from falling. Then, solutions of three dyes were
separately poured into the hydrogel column until the layer was fully submerged, and
the initial concentration of the solutions set at 50 mg/L. The absorbance values of the
filtrate were recorded at regular intervals using a spectrophotometer.

To investigate the adsorption capacity of PAS/aBC-CD hydrogel in real water samples,

five types of water samples were selected for the experiment. These samples included
drinking natural mineral water (MW), laboratory tap water (TW), lake water (LW) from
the school's Dream Creek, and simulated seawater (SW) with a concentration of 30
mg/L NaCl[37]. Additionally, according to the guidelines of the Organization for
Economic Co-operation and Development (OECD) for chemical testing[38], specific
concentrations of CaCl2, MgSO4·7H2O, NaCl, K2HPO4, urea, peptone, and meat extract
were chosen for preparing simulation of textile wastewater. The pH of all samples was
adjusted to be within the range of 6-8 to maintain consistency with previous studies.
The real water samples and simulated water samples were used to prepare dye solutions,
and batch adsorption experiments were conducted at a temperature of 298K.

3. Results and discussion

3.1 The Synthesis and characterization of PAS/aBC-CD hydrogel

3.1.1 The synthesis of PAS/aBC-CD

Figure 1 illustrated the design and synthesis process of PAS/aBC-CD hydrogel. In this
process, cyclodextrin was connected to the surface of porous biochar through ester
bonds, and then crosslinked uniformly in the hydrogel polymer with AA and SSS
polymer chains using MBA crosslinker, resulting in the preparation of porous biochar
composite hydrogel. It was noteworthy that the hydrogel prepared by sol-gel method
possesses abundant pore structure, and the carboxyl and sulfonic acid groups on the
surfaces of AA and SSS polymers are speculated to assemble a large amount of negative
charges, indicating that PAS/aBC-CD hydrogel might have high adsorption capacity
towards cationic dyes.

8
 Figure 1 The design and synthesis process of PAS/aBC-CD

3.1.2 FTIR

In Fourier transform infrared spectroscopy (FTIR) analysis, each chemical bond in a

substance displayed a unique absorption band. The FTIR spectra of biochar (BC),
cyclodextrin-modified biochar (aBC-CD), and hydrogel (PAS/aBC-CD) were shown in
the Figure 2(a). The infrared spectrum of BC showed peaks mainly at 3467 cm-1, 2913
cm-1, 1610 cm-1, and 1322 cm-1, which were attributed to the stretching vibration of -
OH, the stretching and bending vibrations of C-H single bonds, and the stretching
vibration of C=C carbon skeletons, respectively. After β-CD modification, the
characteristic absorption peaks at 1159 cm-1 and 1010 cm-1 correspond to the stretching
vibration of C-OH and the anti-symmetric glycosidic vibration of C-O-C,
respectively[39]. The characteristic peak at 1724 cm-1 was attributed to the stretching
vibration of the grafted ester bond C=O[40]. These results indicated that β-CD had
successfully been grafted onto the surface of biochar through esterification reaction[41].
In addition to the characteristic absorption peaks of aBC-CD, the peaks at 1074 cm-1
and 1005 cm-1 corresponded to the stretching vibration of S=O and the stretching
vibration of S-O single bond, respectively[37,42]. The results could be caused by sodium
styrene sulfonate. The peaks at 1706 cm-1 and 3490 cm-1 corresponded to the
characteristic absorption peaks of the carbonyl group and hydroxyl group on the acrylic
acid carboxyl group, respectively. These results indicated that AA and SSS had
successfully undergone copolymerization.

3.1.3 SEM

SEM was used to investigate the microstructure of BC, aBC-CD, and PAS/aBC-CD

9
hydrogel. As shown in Figure 2(c), biochar exhibited numerous irregular pores on its
surface. After modification with β-CD, some small pores on the biochar surface were
filled with β-CD, while β-CD molecules were also distributed on the inner walls of
large pores. This indicated successful grafting of β-CD onto the biochar surface and the
unique structure of β-CD could increase the functional groups and water affinity of the
biochar surface[37]. Figure 2(e) showed the microstructure of PAS/aBC-CD hydrogel,
which had pore structures with a diameter of approximately 10-50 μm on its surface.
This abundant pore structure significantly increased the specific surface area of the
hydrogel, facilitating the contact between dye molecules and the hydrogel surface and
achieving better adsorption effects.

3.1.4 TGA

In the TGA curve of aBC (Figure 2(b)), the weight loss observed across the entire
temperature range could be attributed to the decomposition of oxygen-containing
functional groups[43]. This indicated that the surface of biochar contained a significant
amount of oxygen-containing functional groups, which enhanced its adsorption
capacity after acidification and oxidation treatment. In the TGA curve of aBC-CD, the
weight loss observed before 100°C was mainly due to the evaporation of free water
adsorbed on the aBC-CD. The weight loss observed in the temperature range of 180°C
to 320°C was primarily attributed to the dehydroxylation of aBC-CD[40]. The weight
loss observed in the temperature range of 320°C to 600°C was mainly attributed to the
thermal decomposition of β-CD[44]. Additionally, it could be observed that the residual
weight of PAS/aBC-CD was significantly smaller than that of aBC. Therefore, these
results indicated that β-CD was successfully grafted onto the surface of biochar through
esterification reaction. In the TGA curve of PAS/aBC-CD, the weight loss in both
temperature ranges was higher than that of aBC. This was mainly due to the
introduction of AA and SSS, which leaded to carbonization of the two copolymers.
These results indicated the successful synthesis of PAS/aBC-CD.

10
 Figure 2 Fourier infrared spectra of BC, aBC-CD and PAS/aBC-CD(a); TGAs of aBC, aBC-CD and PAS/aBC-
CD(b); SEM images of BC(c), aBC-CD(d) and PAS/aBC-CD(e)

3.2 Adsorption experiment

3.2.1 The influence of pH value

This study investigated the effect of pH on dye adsorption. It was known that the charge
density and surface charge of adsorbents could vary with changes in pH[45]. pHpzc of
PAS/aBC-CD hydrogel was measured, and the results (Figure 4(a)) showed that its
pHpzc was approximately 4.74. This meant that when the solution pH was less than 4.74,
the adsorbent will be protonated and carry a weak positive charge, which was
unfavorable for the adsorption of cationic dyes[46]. However, when the solution pH was
greater than 4.74, the adsorbent will be deprotonated and carry a negative charge, which
was favorable for the adsorption of cationic dyes[45]. The study also measured the
amount of dye adsorbed by PAS/aBC-CD hydrogel under different pH conditions.
Under strong acidic conditions, the surface of PAS/aBC-CD hydrogel was positively
charged, and the electrostatic attraction to cationic dyes was not significant, but there
was still a small amount of adsorption capacity. From this, it can be inferred that in the
adsorption process, apart from electrostatic forces, there are other forces at play.[39]. As
the pH increased to alkaline conditions, the negative charge density on the surface of
PAS/aBC-CD hydrogel gradually increased, increasing the number of adsorption sites.
At this point, electrostatic interactions played a major role, and the adsorption capacity
of PAS/aBC-CD hydrogel for cationic dyes gradually increases.

11
3.2.2 Effect of ionic strength

In real textile wastewater, not only dye molecules were present, but also many inorganic
ions. These inorganic ions competed with the adsorption sites of PAS/aBC-CD
hydrogel for dye molecules, thereby affecting the adsorption capacity of dyes. In this
study, Na+ and Ca2+ were selected as analogs for other cations in real water samples.
The results from Figure 3 showed that with the increase of ion concentration, the
adsorption amount of PAS/aBC-CD hydrogel on cationic dyes gradually decreased.
This was because the adsorption sites on the PAS/aBC-CD hydrogel were limited, and
inorganic ions such as Na+ and Ca2+ in the water sample will occupy the adsorption
sites that should have belonged to the dye molecules, thus leading to a decrease in
adsorption amount[47]. When the ion concentration was 0.1 mol/L, the effect of Ca2+ on
the adsorption process was much greater than that of Na+, which indicated that ions
with higher ion strength occupied more adsorption sites and had a greater impact[48]. It
also indicated that electrostatic interactions played an important role in the dye
adsorption process of PAS/aBC-CD hydrogel.

100 MB MG NR Effect of NaCl

80
qe(mg/g)

60
40
20
C(mol/L)
0 0
0 0.02 0.04 0.06 0.08 0.1
-20

qe(mg/g)
-40
-60
Effect of CaCl2 -80
MB MG NR -100

Figure 3 The effect of different concentrations of NaCl and CaCl2 on the Adsorption of MB, MG, and NR cationic
Dyes.

3.2.3 Influence of adsorbent dosage

The relationship between the dosage of adsorbent and its adsorption performance on
dyes was shown in Figure 4(c-e). As the dosage of PAS/aBC-CD hydrogel increased,
the equilibrium adsorption capacity of PAS/aBC-CD hydrogel gradually decreased,
while the removal rate of the three dyes increased. For the specific three dyes, when the
dosage of the adsorbent was 1 mg/10 mL, the adsorption capacity of PAS/aBC-CD
hydrogel for MB, MG, and NR dyes was 450 mg/g, 350.4 mg/g, and 360.6 mg/g,
respectively, and the removal rates were 45%, 35.04%, and 36.06%, respectively. When

12
the dosage was increased to 10 mg/mL, the adsorption capacity for three types of dyes
(MB, MG, and NR) decreased to 97 mg/g, 95 mg/g, and 91 mg/g, respectively; however,
the removal rates increased to 97%, 95%, and 96% for each of the dyes. This
phenomenon could be explained from the perspectives of both the dye and the adsorbent.
Firstly, as the dosage of the adsorbent increases, the dyes could be more fully adsorbed
onto the surface of the adsorbent, and the residual dye concentration gradually
decreased, resulting in an increase in the removal rate of the dye[49]. Secondly, when
the dosage of the adsorbent was small, the adsorption sites on the surface of the
adsorbent were mostly occupied, resulting in a large equilibrium adsorption capacity of
the adsorbent[50,51]. However, as the dosage of the adsorbent increased, the number of
adsorption sites increased, and more adsorption sites remained on the surface of the
adsorbent, leading to a decrease in the equilibrium adsorption capacity of the
adsorbent[52]. Therefore, when the dye concentration was sufficiently high, PAS/aBC-
CD hydrogel could achieve a larger equilibrium adsorption capacity.

Figure 4 Equilibrium adsorption capacity(b) and zero point charge(a) of MB, MG, and NR by PAS/aBC-CD
hydrogel under different pH conditions; Equilibrium adsorption capacity and removal efficiency of MB(a), MG(b),
and NR(c) by PAS/aBC-CD at different dosages of PAS/aBC-CD hydrogel.

13
3.2.4 Adsorption model analysis

3.2.4.1 Adsorption kinetics

PAS/aBC-CD hydrogel was investigated for its adsorption kinetics of three dyes, and
the fitting results and parameters were presented in the Figure 5 and Table S1,
respectively. The adsorption of dyes onto hydrogel initially occurs rapidly, followed by
a gradual retardation. This phenomenon could be attributed to the abundant adsorption
sites on the surface of the hydrogel, allowing for rapid capture of surrounding cationic
dye molecules upon initial contact[53]. As the adsorption process progresses, most of the
active sites on the hydrogel surface become occupied, resulting in a decrease in
adsorption rate until reaching an adsorption equilibrium state. The pseudo-first-order
and pseudo-second-order kinetic models were chosen to fitted the adsorption process
of hydrogel, as shown in the Figure 5 (a, b). The kinetic analysis showed that the
adsorption of the three cationic dyes prepared by hydrogel all conformed to the pseudo-
second-order model. Specifically, the R2 values of the adsorption data fitted by this
kinetic model were between 0.992 and 0.999, indicating the adsorption process of
PAS/aBC-CD hydrogel was mainly based on chemical adsorption[54]. The limiting
process and mass transfer mechanism of particle diffusion and liquid film diffusion
were analyzed. As shown in the Figure 5 (c, d), the mass transfer process could be
divided into three stages. The first stage was boundary layer diffusion, and the larger C
value indicated a greater influence of the boundary layer on the mass transfer of the
dye[55]. The second stage was particle diffusion, where the dye molecules gradually
diffuse into the interior of the hydrogel[56]. The third stage mainly showed that the dye
molecules were adsorbed onto the active sites of the hydrogel, and the slope of the curve
was close to 0, indicating a slower reaction rate and ultimately reaching equilibrium[57].
The relationship between the slopes of the curves in the three stages was Kid1> Kid2>
Kid3. This indicated that the arrival of MB, MG and NR dyes at the surface of the
hydrogel was a fast process, followed by a slow process of reaching the interior of the
hydrogel, and finally reaching an adsorption equilibrium[58]. The curves in the three
stages did not pass through the origin, indicating that particle diffusion was not a single
limiting step but a composite system containing multiple rate-limiting steps[59]. The
fitting curve of liquid film diffusion also did not pass through the origin, indicating that
liquid film diffusion also existed in the adsorption process of the three dyes[60].

14
 Figure 5 Fitting of pseudo-first-order(b) and pseudo-second-order kinetic(a) models for the adsorption of MB,
MG, and NR by PAS/aBC-CD hydrogel, and liquid film diffusion model(c) and intra-particle diffusion model(d)
of adsorbent

3.2.4.2 Isothermal analysis

This study investigated the adsorption behavior of PAS/aBC-CD hydrogel towards

three cationic dyes, namely MB, MG, and NR. The results indicated that the adsorption
capacity of the PAS/aBC-CD hydrogel gradually increased as the concentration of
cationic dyes increased, while the removal rate decreased. This was because the
increase of dye concentration overcame the mass transfer resistance between the
aqueous and solid phases, increased the driving force, and consequently enhanced the
adsorption capacity of the hydrogel. Moreover, as the temperature increased, the
diffusion rate of dye molecules accelerated, allowing them to reach adsorption
equilibrium more quickly and leading to an increase in adsorption capacity[46].

The adsorption behavior of PAS/aBC-CD hydrogel towards MB, MG, and NR was
analyzed using isotherm models such as Freundlich and Langmuir. The results showed
that the correlation coefficients R2 for the Freundlich model range from 0.875 to 0.982,
while those for the Langmuir model range from 0.998 to 0.999. Thus, the Langmuir
equation could be used to described the adsorption behavior of cationic dye molecules
on the PAS/aBC-CD hydrogel. Additionally, the adsorption process could be described
as primarily involving single-layer adsorption[61]. The dimensionless constant
separation factor RL was commonly used to evaluate the effectiveness of the adsorption
15
process. Table S2 showed that the RL values were between 0.02 and 0.86, indicating
that the adsorption of the three cationic dyes by PAS/aBC-CD hydrogels was
favorable[46].

Table S3 displayed the comparison of adsorption performance of some hydrogel

adsorbents for cationic dyes over the past two years. It could be observed that
PAS/aBC-CD hydrogel exhibited outstanding adsorption capacity, indicating that it
could be an excellent adsorbent for cationic dyes with ultra-high adsorption capacity.

3.2.4.3 Thermodynamic analysis

According to the Van't Hoff curve obtained from thermodynamic analysis shown in
Figure 6(d), the values of ∆S and ∆H could be obtained by solving the corresponding
slope and intercept of the equation[53]. The thermodynamic parameters provided in the
Table S4 showed that ∆G was always negative, indicating that the adsorption of the
three dyes by PAS/aBC-CD hydrogel was spontaneous and in accordance with
thermodynamic behavior[62]. In addition, as the temperature increased, the value of ∆G
decreased, indicating that high temperature was favorable for the adsorption process. It
was worth noting that the values of ∆H were always positive, with values of 6.47, 6.82,
and 44.89 kJ/mol, indicating that the adsorption process of dyes on PAS/aBC-CD
hydrogel was endothermic. At the same time, the values of ΔS were always greater
than zero, with values of 40.32, 51.54, and 158.61 J/(mol·K), indicating that the
randomness of the solid-liquid interface increased during the adsorption of cationic
dyes on PAS/aBC-CD hydrogel, which overall results in an increase in entropy[63].

(a) (b)
2000 1800
1600
1400
1500
1200
qe(mg/g)
qe(mg/g)

MB 1000
1000
800
MG
600
500
400
25℃ 35℃ 45℃
25℃ 35℃ 45℃ 200 Langmuir Langmuir Langmuir
0 Langumuir Langumuir Langumuir 0 Freundlich Freundlich Freundlich
Freundlich Freundlich Freundlich
-200
0 500 1000 1500 2000 2500 0 500 1000 1500 2000 2500 3000
Ce(mg/g) Ce(mg/g)

16
 (c) (d)
1400 Thermodynamic
3.5
1200
3.0
1000
2.5
800
qe(mg/g)

lnKc
NR 2.0
600
1.5 MB
400 MG
NR
200 25℃ 35℃ 45℃ 1.0
Langmuir Langmuir Langmuir
Freundlich Freundlich Freundlich 0.5
0

0 500 1000 1500 2000 2500 3000 3.00 3.05 3.10 3.15 3.20 3.25 3.30 3.35 3.40
Ce(mg/g) 1000/T(K-1)

Figure 6 Simulation of Frenundlich and Langmuir models and thermodynamic statistical graphs(d) for the
adsorption of three dyes, MB(a), MG(b) and NR(c), on PAS/aBC-CD hydrogels

3.2.5 Application experiment of adsorbent

3.2.5.1 Repeatability of adsorbent

The cyclic regeneration property was an important indicator for evaluating the
performance of adsorbents. During the cyclic regeneration process, the adsorbent
needed to undergone a series of adsorption and desorption processes. If the adsorption
capacity and removal rate of the adsorbent could remain stable over multiple cycles,
then the adsorbent's repeatability would be high, thereby reducing the cost of
wastewater treatment. The experimental results in Figure 7(a) indicated that the
PAS/aBC-CD hydrogel's removal rate for the three dyes remained about 98%, after five
cycles, indicating that PAS/aBC-CD hydrogel had a high repeatability. It was worth
noting that during the cyclic regeneration process, some dyes might not be completely
desorbed during the desorption process, resulting in some adsorption sites being
prematurely occupied, causing a slight decrease in removal rate[64].

3.2.5.2 Column adsorption

In order to further investigated the applicability of PAS/aBC-CD hydrogel, column

adsorption was selected to explore the adsorption performance of the hydrogel (Figure
7(b)). The hydrogel was used as the filling layer of the adsorption column, and a dye
solution with a concentration of 50 mg/L was added to the gel column and continuously
filtered out. At the same time, the concentration of the dye in the filtered liquid was
measured at regular intervals[65]. The experimental results showed that with the progress
of column adsorption, the absorbance and concentration of the three dyes in the filtered
liquid gradually decreased. After about 120 min, the removal rates of NR, MB, and MG
in the filtered liquid reached 97.42%, 96.67%, and 97%, respectively. Changes in the
absorption spectrum during the adsorption process indicated that the uniformly filled
gel layer provided many sites for dye adsorption, allowing the dyes to be rapidly
removed from the aqueous solution. This indicated that PAS/aBC-CD hydrogel had
17
excellent potential for practical applications.

3.2.5.3 Real water samples adsorption

To investigated the potential of adsorption process in practical applications, this study

examined the adsorption capacity of MB, MG, and NR dyes in real water samples. The
experiments were conducted under the following conditions: [PAS/aBC-CD] = 1
mg/mL, [dye] = 100 mg/g, with constant temperature shaking for 24 hours. The results
(Figure 7(c)) showed that PAS/aBC-CD hydrogel could be a highly effective adsorbent.
Although the effectiveness of the adsorbent was affected by the complex water quality
factors in simulating textile wastewater, leading to a more significant decrease in
adsorption capacity, PAS/aBC-CD hydrogel still exhibited high adsorption capacity in
the other four water samples. This suggested that PAS/aBC-CD hydrogel has broad
potential applications in dye wastewater treatment.

3.2.5.4 Binary co-adsorption

The above results indicated that the adsorption of dyes by PAS/aBC-CD hydrogels was
mainly dependent on electrostatic forces. Therefore, the adsorption capacity of
hydrogels in dye/CrO42- mixed systems was investigated. The promoting adsorption
capacity of the hydrogel for both pollutants was expressed by 𝑅𝑞, which could be
determined by the equation：

𝑞𝑒
Rq = (12)
𝑞𝑠

where q𝑒 represents the equilibrium adsorption capacity of PAS/aBC-CD hydrogel for

a single dye system, and 𝑞𝑠 represented the equilibrium adsorption capacity of
PAS/aBC-CD hydrogel for the dye/CrO42- mixed system.

Figure 7(d) showed the 𝑅𝑞 values at different CrO42- concentrations. 𝑅𝑞 greater than 1
indicated that CrO42- promoted the adsorption of dye molecules. Moreover, as the
concentration of CrO42- increased, the 𝑅𝑞 value increased, indicating a stronger
promoting effect. This could be explained by the fact that, in the adsorption process, in
addition to electrostatic forces, there were also host-guest interactions between
cyclodextrin and the dye molecules, as well as the pore filling effected on the surface
of the biochar and hydrogel. When CrO42- was adsorbed by these forces, the negative
charge on the surface of CrO42- had a certain electrostatic attraction to the dye molecules,
thereby promoting the adsorption of cationic dyes by PAS/aBC-CD hydrogel. It could
also be observed that as the concentration of CrO42- increased, the increase in R𝑞
values became increasingly slow. The result may be due to the fact that the adsorption
of CrO42- tends to reach equilibrium under the testing conditions, and the promoting
effect also exhibits a stable state[66,67].

18
Figure 7 Repeatability study of the adsorption of MB, MG, and NR dyes by PAS/aBC-CD hydrogel(a); adsorption
of NR dyes by PAS/aBC-CD hydrogel in column process(b); the adsorption capacity of PAS/aBC-CD for MB,
MG, and NR dyes in different water samples(c); Rq data plot for the co-adsorption of CrO42- and dye in a binary
system(d)

3.2.6 Adsorption mechanism analysis

3.2.6.1 The XPS analysis before and after adsorption

As shown in Figure S2 (a-c), the molecular size diagrams of the three dyes are presented.
It can be observed that the maximum edge length of the dye molecules is 15.68 Å (1.568
nm). Studies have shown that the pore size of an effective adsorbent should be 1.3 to
1.8 times the diameter of the target adsorbate[68]. Therefore, it is advantageous for the
adsorbent to have a pore size greater than 2 nm for the adsorption of dyes. Meanwhile,
SEM images of PAS/aBC-CD reveal that the minimum pore diameter of the original
biochar is 36.3 nm. Consequently, dye molecules can adequately enter the pores and be
captured by adsorption sites.

By analyzing the X-ray photoelectron spectroscopy (XPS) of PAS/aBC-CD hydrogel

before and after adsorption, the adsorption mechanism of PAS/aBC-CD hydrogel was
investigated (Figure 8). Before adsorption, the O1s spectrum exhibited two binding

19
energy peaks at 532.13 eV and 531.38 eV, attributed to C-O/C=O and S-O/S=O groups
[40,55]. After MB, MG, and NR were adsorbed onto the surface of the PAS/aBC-CD

hydrogel, the binding energy peaks for C-O/C=O shifted to 532.53 eV, 533.23 eV, and
531.73 eV, while those for S=O shifted to 531.53 eV, 531.68 eV, and 531.13 eV,
respectively. Meanwhile, the peak area of C-O/C=O increased relatively after
adsorption. This may be caused by electrostatic interactions between -COOH and -
SO3H groups and dye molecules[56]. Additionally, hydrogen bonding between
functional groups and the hydrogel can also facilitate dye adsorption on the hydrogel
surface. In the N1s spectrum, two binding energy peaks were observed on the surface
of the PAS/aBC-CD hydrogel before adsorption, corresponding to -NH2/-NH (398.86
eV) and graphite N (399.67 eV) structures [47]. After the adsorption of MB, MG, and
NR onto the surface of the PAS/aBC-CD hydrogel, the binding energies of the original
-NH/-NH2 peaks shifted to 398.48 eV, 399.63 eV, and 398.48 eV, respectively, while
graphite N shifted to 402.58 eV, 401.53 eV, and 401.63 eV, and the peak areas also
changed to some extent. These results indicate that the dyes were adsorbed onto the
surface of the hydrogel. According to literature reports, nitrogen has a high
electronegativity, and the electron density of graphite decreases with the introduction
of nitrogen, forming an electric potential difference with the electron density of the
aromatic ring in the dye, thereby generating π-π stacking forces between them.[69,70].

20
 Figure 8 XPS data graphs of PAS/aBC-CD before and after adsorption of three dyes (MB, MG, and NR)

3.2.6.2 Analysis of FTIR before and after adsorption

As shown in the Figure 9, the infrared absorption peaks of PAS/aBC-CD hydrogel

changed before and after the adsorption of cationic dyes. After adsorption, the
characteristic absorption peaks of PAS/aBC-CD at 1700 cm-1 shifted to 1735 cm-1, 1718
cm-1, and 1727 cm-1, indicating that the -COOH group played an important role in the
adsorption process of cationic dyes[65]. The characteristic absorption peak of -OH at
3490 cm-1 shifted to 3509 cm-1, 3478 cm-1, and 3478 cm-1, suggesting that there was an
electrostatic interaction and hydrogen bond between the hydroxyl groups on PAS/aBC-
21
CD and the cationic dyes during the adsorption process[71]. In other words, the O-H on
PAS/aBC-CD made a significant contribution to the capture of MB molecules during
the adsorption process. The characteristic absorption peak of the sulfonic acid group
shifted from 1074 cm-1 to 1087 cm-1, 1106 cm-1, and 1093 cm-1, indicating that the
sulfonic acid group participated in the adsorption process of cationic dyes, which was
in line with the initial design concept[41]. The characteristic absorption peak of the
aromatic ring shifted from 1615 cm-1 to 1627 cm-1, 1616 cm-1, and 1625 cm-1, which
may be due to the fact that both PAS/aBC-CD adsorbent and the three dyes (MB, MG,
and NR) have planar hexagonal ring structures, which easily form π-π stacking
interactions[72].

1093
hydrogel-NR 1727
3478

1625

hydrogel-MG 1718
3478

1106

1616

1087
3509

1735
hydrogel-MB

1627
3490

hydrogel 1700
1615
1074
C=O C=C
-OH S=O

4000 3500 3000 2500 2000 1500 1000 500

Wavenumbers(cm-1))
Figure 9 FTIR Spectral Analysis of PAS/aBC-CD Hydrogel Before and After Adsorption of Three Cationic Dyes
(MB, MG, and NR)

Based on the characterization analysis of PAS/aBC-CD before and after adsorption, it

could be concluded that electrostatic interaction plays a major role in the adsorption
process. In addition, there were other forces at play, such as hydrogen bonding, pore
filling, π-π stacking, and host-guest interactions. Firstly, AA and SSS could provide
strong electrostatic interactions by protonation and deprotonation of sulfonic acid and
carboxyl groups at different pH values. Furthermore, dye molecules had abundant
aromatic structures that could be adsorbed onto the surface of the hydrogel through π-
π interactions. The surface of the biochar contained abundant N and O functional groups,
which could provide attachment points for hydrogen bonding interactions. SEM images
22
showed that both the PAS/aBC-CD hydrogel surface and the biochar surface have
abundant pores, which increased the contact opportunity between the hydrogel and the
dye, allowing the dye molecules to be fixed in the pore channels. β-CD had a
hydrophobic cavity and a hydrophilic outer surface, which could adsorb dye molecules
through host-guest interactions. The adsorption mechanism was shown in the Figure
10.

Figure 10 The adsorption mechanism of PAS/aBC-CD hydrogel for MB, MG, and NR

Conclusions
In this study, a simple composite method was employed to prepare a biochar-based
composite hydrogel adsorbent, achieving efficient adsorption of cationic dyes.
Additionally, the issue of the poor separability of powdered biochar was addressed. The
maximum adsorption capacities of MB, MG, and NR dyes were found to be 1494 mg/g,
1182 mg/g, and 1031.6 mg/g, respectively, which are higher than those of most biochar
adsorbents. After several cycles of elution with alkali, the adsorbent maintained 98%
of its adsorption capacity, even after five regeneration cycles. Furthermore, simulated
column adsorption experiments demonstrated its significant potential for practical
applications. It is worth noting that synergistic adsorption experiments have shown that
CrO42- ions can serve as bridges for the co-adsorption of cationic dyes. Mechanistic
studies indicate that the adsorbent primarily relies on electrostatic interactions, π-π
stacking, hydrogen bonding, host-guest interactions, etc., for the adsorption of cationic
dyes. However, further research is needed for a deeper analysis of the adsorption
mechanisms. This work provides a promising practical method for the removal of dyes
from water, highlighting the outstanding adsorption capacity and effective regeneration
capability of the adsorbent. The outstanding adsorption capacity and effective
regeneration ability of the adsorbent highlighted in this study provide a promising
practical method for the removal of dyes from water.
23
In addition, although the materials used in this study are readily available under
laboratory conditions, the high cost of freeze-drying and the inherent risks associated
with certain reagents during the preparation process suggest that further research will
be needed to optimize experimental procedures. Furthermore, exploring the removal of
more types of organic pollutants to increase the applicability of the materials.

24
CRediT authorship contribution statement

Jie Wu: Methodology, Investigation, Writing – original draft, Software.

Keran Li: Conceptualization, Supervision, Resources.

Xin Li: Paper revision

DaHua Zhou: Paper revision

Baidan Li: Paper revision

Declaration of Competition Interest

The authors claim that they have no known competing economic interests or personal
relationships that may affect the work reported in this paper.

Acknowledgments

The work was supported by the Natural Science Foundation of China (52004234),
International Science and Technology Cooperation Project from Chengdu Municipal
Government (2022-GH02-00025-HZ), Opening Project of State Key Laboratory of
Polymer Materials Engineering (Sichuan University) (Grant No. sklpme2020-4-14),
and Cooperation Project between Southwest Petroleum University and Nanchong City
(SXHZ047).

25
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Preparation of porous composite hydrogel with ultra-high cationic

dye adsorption capacity based on biochar: adsorption behaviors and

mechanisms

Keran Li a, b,*, Jie Wu a, Xin Lia, Baidan Lia, Dahua Zhou c ,*

aCollege of Chemistry and Chemical Engineering, Southwest Petroleum University,

Chengdu, 610500, PR China
bState Key Laboratory of Polymer Materials Engineering, Sichuan University,
Chengdu, 610500, PR China
c-Chongqing Intelligent Technology, Chinese Academy of Green and Intelligent
Technology, Chinese Academy of Sciences, Chongqing 400714, China

Keran Li - College of Chemistry and Chemical Engineering, Southwest Petroleum

University, Chengdu, 610500, Sichuan, China; Tel: +86 028 83037306; fax: +86 028
8303 7305; E-mail address: [email protected]

31
Dahua Zhou - Chongqing Intelligent Technology, Chinese Academy of Green and
Intelligent Technology, Chinese Academy of Sciences, Chongqing 400714, China;
Email: [email protected]

Declaration of Competition Interest

The authors claim that they have no known competing economic interests or personal
relationships that may affect the work reported in this paper.

Preparation of porous composite hydrogel with ultra-high cationic

dye adsorption capacity based on biochar: adsorption behaviors and

mechanisms

Keran Li a, b,*, Jie Wu a, Xin Lia, Baidan Lia, Dahua Zhou c ,*

aCollege of Chemistry and Chemical Engineering, Southwest Petroleum University,

Chengdu, 610500, PR China
bState Key Laboratory of Polymer Materials Engineering, Sichuan University,
Chengdu, 610500, PR China
c-Chongqing Intelligent Technology, Chinese Academy of Green and Intelligent
Technology, Chinese Academy of Sciences, Chongqing 400714, China

Keran Li - College of Chemistry and Chemical Engineering, Southwest Petroleum

University, Chengdu, 610500, Sichuan, China; Tel: +86 028 83037306; fax: +86 028
8303 7305; E-mail address: [email protected]

Dahua Zhou - Chongqing Intelligent Technology, Chinese Academy of Green and

Intelligent Technology, Chinese Academy of Sciences, Chongqing 400714, China;
Email: [email protected]

Graphical Abstract

32
 Preparation of porous composite hydrogel with ultra-high cationic

dye adsorption capacity based on biochar: adsorption behaviors and

mechanisms

Keran Li a, b,*, Jie Wu a, Xin Lia, Baidan Lia, Dahua Zhou c ,*

aCollege of Chemistry and Chemical Engineering, Southwest Petroleum University,

Chengdu, 610500, PR China
bState Key Laboratory of Polymer Materials Engineering, Sichuan University,
Chengdu, 610500, PR China
c-Chongqing Intelligent Technology, Chinese Academy of Green and Intelligent
Technology, Chinese Academy of Sciences, Chongqing 400714, China

Keran Li - College of Chemistry and Chemical Engineering, Southwest Petroleum

University, Chengdu, 610500, Sichuan, China; Tel: +86 028 83037306; fax: +86 028
8303 7305; E-mail address: [email protected]

Dahua Zhou - Chongqing Intelligent Technology, Chinese Academy of Green and

Intelligent Technology, Chinese Academy of Sciences, Chongqing 400714, China;
Email: [email protected]

33
Highlights

1. Simple composite method to encapsulate biochar in a gel network.

2. CrO42- as a bridge for synergistic adsorption of dyes.

3. Column adsorption simulation to explore the potential of adsorbents

4. High cyclic stability of the adsorbent.

34